Benzothiazole-2-sulfenamide type cure accelerators for mercapto polymers



United States Patent 3 487 052 BENZOTHIAZOLE-Z-SlJLI ENAMIDE TYPE CURE AC'CELERATORS FOR MERCAPTO POLYMERS Edward G. Millen, Princeton, N.J., and Paul A. Koons,

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agent may be stored in one package with a suitable accelerator being stored in a second package.

Liquid polymers containing a plurality of SH groups may be cured with compounds which react with the --SH Yardley, Pa., assignors to Thiokol Chemical Corpo- 5 gr ps in such a Way as to condense or unite lower moration, Bristol, Pa., a corporation of Delaware lecular weight segments to form higher molecular weight N0 Dlawihg- Filed 1966, 601,337 solid materials. Commonly such polymers are oxidatively Cosg 23/20 cured with organic or inorganic oxidizing agents whereby 26079 14 Clams pairs of SH groups in the liquid polymers are oxidized to SS groups thus promoting the formation of solid higher molecular weight materials. Often the reaction ABSTRACT OF THE DISCLOSURE between an oxidizing agent and an --SH containing poly- Liqhid P y containing g p are cured mer is too slow for practical purposes, particularly at with inorganic OXidiZihg agents in the Presence of behzoroom temperatures, and the addition of an accelerator is thiozole-sulfenamide type compounds W h have all 15 required. Common accelerators which have been used in accelerating of synergistic efiect on the curing reactiohcombination with oxidizing agents for the curing of liquid SH containing polymers are elemental sulfur and alkaline compounds such as ammonia and amines BACKGROUND OF THE INV e.g. hexamethylene tetramine, 2,4,6-tris(dimethylamino- This invention relates to novel curable liquid SH methyl) P mbutylamme containing polymer systems and to the cured products that SUMMARY OF THE INVENTION be produced i p More par-tlcl-llarly thls m- It has now been found that certain organic sulfur-convention relates to oxidatively curable llquid SH cont d t 1 t t l mer s Stems utilizing thiazole and thiazoline ammg compoun 5 con almng a 121.20 e i S i tammg Po y y ture are useful as co-curlng agents in combination with compounds as co'cunng agents m combmanon Wlth or anic and inor anic ox en-containin curin a ents organic and inorganic oxygen-containing curing agents. the cure of conglginin 1i id 1 g i Liquid SH containing polymers are used extensively 0 g p0 i in sealants and caulking compositions, especially in the c cunng agen S m seine cases ac as acce era ors they speed up the curing process. In other cases, they bulldlng and automotlve industries, for castlngs, e.g. a e t h th th k lid rocket ro ellants' for leather and textile impregnatpp 0 ave Synerg1s.1c m at ey P p possible a cure of the llqllld polymers with certaln agents; for adheslves coatmgs oxidizing agents which alone do not effect any appreci- Depehdlhg UP011 the requlrements of the Partlcular able cure. While the effect of the co-curing agents used application, and the nature 9 the cure f h the in the present invention may be shown at elevated tem- Pollents of the curable hquld contammg polymerj peratures as well as at room temperature, the most sursystems y bh Packaged as Or -P Systems: prising results are obtained at room temperature. 'P Systems are those in which all the components It is an object of this invention, therefore, to provide a are stored together with no appreciable reaction taking variety f novel curing Systems for containing Place until activated by some external Influence Such as liquid polymers suitable for use at room temperature or heat ,surface application Of curing accelerators, exposure 40 elevated temperature in oneart or two.part composito moisture in the atmosphere, etc. Such a moisture-actitions vatable composition is described in US. 3,225,017.

'IWvo-part systems are those in which the reactive com- DESCRIPTION OF THE PREFERRED ponents are stored in separate packages and tsmbinea"" I V I EMBODIMENTS a just prior to use. This type of system is most common 49 The organic sulfur-containing co-curing agents useful and usually involves the storage of liquid polymer and in the present invention are compounds containing curing agent in separate packages, as for example Pb thiazole or thiazoline rings having a sulfur bearing group cured liquid polyalkylene polysulfide compositions. In attached to the ring in the 2-position.

another package arrangement, the polymer and curing Representative compounds are the following:

Chemical name Structure 2mercaptobenz0thiazole S O-SH N Benzothiazolyl disulfide S s\ C .S S C N-oxydiethy enebenzothiazole-Z- S sulfenamide. 0 Hz- 0 H2 CS-N \N/' CHrlHg Chemical name Structure N -cyclohexylbenzothiazole-2- S sulfenamide. H 0H2CH2 CS-NCH CH CHz-OHz N,Ndiisopropylbenzothiazole-z- C H;

sulfenamide. /S Cg C-S-N CH CH-OH Zinc salt of 2-mercaptobenzothiaz01e..-.. S

Zn C S 1,3-bis(2-benzothiazolylmercaptomethyl) S urea. =0

O S C Hz-NH 2-mercaptothiazoline H 0- S (l C S H N,N-diethylbenzothiazole-2- S sulfenamide.

N( zHs)2 2- (2,fi-dimethyl-i-morpholinothio)- 0 H benzothiazole. S OH 0g O- S N\ /O CHz-(JE The benzothiazole-2-sulfenarnides type compounds contemplated herein correspond to the general formula The benzothiazole co-curing agents of the present invention may have substituents such as halogen, alkyl, nitro groups, etc. on the benzene or heterocyclic ring. The organic sulfur-containing co-curing agents, according to the present invention, may each be used singularly or in various combinations with one another.

The oxidizing agents, whose curing action on liquid SH containing polymers may be accelerated or enhanced by the above mentioned types of sulfur-containing compounds in accordance with the present invention, include inorganic oxides such as ZnO, PbO, MgO, CaO, BaO, Sb203, Sb205, AS203, AS205, CI203, C110, COO, P133104, FeO, Fe203, Fe O Z1102, M1102, Mggog, P1302, C302, Ba0 8e0 TeO and Li O organic peroxides such as dicumyl peroxide, benzoyl peroxide, stearoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, urea peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and t-butyl perbenzoate; chromates and dichromates such as sodium, potassium, zinc, lead, and ammonium chromates and dichromates; permanganates such as potassium permanganate and barium permanganate; iodates such as potassium iodate; organotin compounds such as dibutyl tin oxide; organic nitro compounds such as dinitrohenzene, trinitrobenzene, and o-nitroanisole; quinoid compounds such as p-quinone dioxime, dimethylglyoxime, quinone and other dioximes; sodium carbonate peroxide; and sodium perborate. The choice of an oxidizing agent is based on its overall performance with respect to a number of requirements including (a) cost of oxidizing agent, (b) stability of oxidizing agent in the formulation, (c) rapid but controllable cure rate, (d) heat stability of the cured polymeric product, (e) lack of adverse efiect on adhesion properties, and (f) elastomeric composition. The oxidizing curing agents, according to the present invention, may be used singularly or in various combinations with one another.

The polymers which may be cured by the co-curing systems of the present invention are, generally, polymers containing a plurality of SH groups, such as,

(A) Liquid polysulfide polymercaptan polymers such as described in US. Patent 2,466,963; I

(B) Liquid polysulfide polymers containing a plurality of -SSH groups such as described in US. Ser. No. 290,- 637 filed June 26, 1963, now abandoned;

(C) Liquid SH terminated polyethers such as SH terminated polypropylene glycol as disclosed in US. Patent 3,258,495;

(D) SH terminated hydrocarbon polymers such as SH terminated polybutadiene (Chem. and Eng. News,

Apr. 4, 1966, p. 37), .SH terminated butadiene/acrylonitrile copolymers and the alkanepolythiol, aralkanepolythiol, and arenepolythiol polymers disclosed in US. Patents 2,230,390, 2,436,137, and 3,243,411;

(E) Liquid SH terminated polyurethanes such as disclosed in US. patent application Ser. No. 484,097, filed Aug. 31, 1965;

(F) Liquid SH terminated poly(alkylene sulfide) polymers as disclosed in US. Patents 3,056,841 and 3,070,580;

(G) Other polythiol polymers such .as disclosed in US.

patent applications Ser. No. 484,105, Ser. No. 484,118, naw abandoned, and Ser. No. 484,122,all filed Aug. 31, 1965.

The SH containing polymers, according to the present invention, may be used singularly or in various combinations with one another.

clays, aluminum powder, iron oxide, rayon fioc, etc., may be added if desired. In general, these additives decrease the elongation and increase the Shore hardness, toughness and tensile strength of the cured polymer based systems.

Other additives such as plasticizers e.g. chlorinated biphenyls and adhesive additives e.g. silane, phenolic and epoxy resins may be used in accordance with standard practice in the art.

The following examples illustrate the present invention but are not intended as a limitation on the scope thereof.

In the examples, the term no cure is used to indicate that no apparent change in viscosity occurred. The term cure indicates that the cured product had a Shore A hardness of approximately 25 or greater, The term soft cure is used to describe a cured state intermediate between cure and no cure. The cures at 75 F. were carried out under ambient conditions of humidity. The cures at 180 F. were effected in a standard convection oven.

Examples 1-4 In Examples 2-4, a group of thiazole and thiazoline compounds were each used at two cure temperatures as a co-curing agent in combination with zinc peroxide to cure a liquid polysulfide polymer, designated as LP-31, which may be represented by the formula:

The polymer is essentially linear with a small amount of branching or cross-linking. It has an average weight of 7500 and a viscosity of 800-1400 posies at 25 C.

Example 1 is a control using only zinc peroxide as I the curing agent. In each case, the thiazole compound accelerated the cure of the polymer as compared with the control. The cure results are listed in Table I. The cure formation used in each case, by Weight, was 25 parts of LP -31, 1.5 parts of zinc peroxide and 1 part of the co-cunng agent.

4 Z-mercaptobenzothiazole Soft cure in 5 days. Cure in 1 hr.

The amount of oxidizing curing agent and sulfur-containing co-curing agent employed in accordance with the present invention may vary substantially depending upon the specific combination of polymer, curing agent and c0- curing agent employed.'In general, per hundred parts of liquid SH containing polymer, the amount of curing agent used would be about 1 to 20 parts and the amount of sulfur-octaining co-curing agent used would be about 1 to 10 parts.

The ingredients of the compositions of the present invention may be combined in any of the conventional methods known in the art such as in a three roll paint mill. If desired, and depending upon the work-life requirements for any particular use, the ingredients may be combined in a one-part system or may be separated in two or more parts so that the curing agent and/or accelerator are in one package or container and the polymer is in another package or container.

As shown in the examples below, some of the systems of the present invention are suitable for room temperature curing and others for heat activated curing or both.

The physical and chemical propertiesof the cured compositions of the present invention may be varied according to the method of application and the specific use intended. Fillers, pigments and reinforcing agents such as titanium dioxide, calcium carbonate, carbon black, silicon dioxide,

Examples 5 and 6 In Example 6, Zetax was used as a co-curing agent with barium manganate to cure LP-31 liquid polysulfide polymer. Example 5 is the control using only barium manganate as the curing agent. The cure formulation used was, by weight, 25 parts of LP-31, 2 parts of barium manganate and 2 parts of the zinc salt of Z-merca-ptobenzothiazo e.

TABLE II Example 5 6 Cure results obtained at 75 N o cure in 30 days Soft cure in 14 days.

0111;?) 5%8111125 obtained at N o cure in '1 days... Soft cure in 4 hrs.

Examples 7-10 oxidizing agent was used asv a curing agent for the polymer used in Examples 8 and 10. In both cases, the cocuring agent exhibited an accelerating or synergistic effeet as compared with the cure using the oxidizing agent 7 8 alone. The formulations given in the table are presented parts by weight of titanium dioxide, 3 parts by weight inparts by weight. of precipitated, hydrated silica, an inorganic oxidizing TABLE 111 Example 7 8 9 10 KI a. Benzothlazolyl disulfide.

N-oxydiethylenebenzothiazole-2-su1- 2.

fenamlde. Cure results obtained at 75 F Noi cure in 5 so cure in 1 No cure in 5 Cure in 3 hrs.

3Y5. l. 8Y8. Cure results obtained at 180 F Soft cure in 1 Cure in hr" Cure in 5 Cure in i4 hr.

day. days.

Examples 1144 agent and 2 parts by weight of a thiazole compound as co-curmg agent as shown in Table VI.

In Examples 12 and 1 two of the curing systems ac- TABLE VI cording to the present lnvention were used to cure a O xidizing liquid terminated butadiene/acrylomtrile copoly agent ms Cum results mer. This copolymer contains about 24% acrylonitrile Ex. Thiazole compound bywelg t) obtained at 75 F. and has a VIOSCOSHY of 35,000 cps. and a specific gravity 21 None 7 M110, (6) soft cumin 4 days of 0.98 at C. 25 22 N- ydi ti lor i obenz MnO; 6 Soft cure in 1 day.

E m 11 and 13 m whlch only the 23 N-eyelohexylbenzo-thiazole- Mn0(6) CureinZdays. oxidlzing agent was used as the curing agent for the same Z-Sulfenamide. copolymer. In all cases the co-curing agent exhibited an 2 5:: ggg g a ggggg; 83525; accelerating or synergistic effect as compared with the thiazole-Z-sultenamide. cure using the oxidizing agent alone. The formulations given in the table are presented in parts by weight. In each of Examples 16-20, 22, 23, and 25, the com- TABLE IV Example 11 12 13 14 Formulation:

urea. N-cyelohexylbenzothlazole-Z-stilfenamide 2. Cure results obtained at 75 F N o cure in Soft cure in Soft cure in 7 days. 23 days. 5 days. Cure results obtained at 180 F Cure in 7days. Bog; sure in Cure in 5 hrs.

Examples 15-25 bination of oxidizing agent with a thiazole co-curing agent produced a faster cure :at 75 F. than did the oxidizing agent alone.

As used throughout the text, the term liquid with respect to defining the polymer means that the polymer is pom-able at room temperature (25 C.).

A filled liquid polysulfide polymer system was tested with various combinations of co-curing agents as shown in Table V and VI. The polymer designated as LP-32, 5 may be represented by the formula:

HS(C H O-CH OC H S-S) We claim:

C H. OCH O-C H SH 1. A curable composition comprising y (A) at least one liquid polymer containing a plurality i gg i giz gg gfg f of 4000 and a v15 of SH groups and selected from liquid polysul- In Examples 1540, 100 parts by Weight of LP 32 fide polymercaptan polymer, llqllld SH terminated polypropylene glycol polymer, and liquid SH terminated butadiene/acrylonitrile copolymer,

(B) at least one oxidizing curing agent selected from the group consisting of inorganic metal oxides, chromates, permanganates, iodates and perborates,

were mixed with 30 parts by weight of calcium carbonate,

10 parts by weight of titanium dioxide, 3 parts by weight of precipitated, hydrated silica, 10 parts by weight f ZnO and 2 parts by weight of oo-curing agents shown in Table V. The control contained ZnO as the only curing agent and (C) a benzothiazole-2-sulfenamide having the general TABLE V formula Ex. Cure results obtained at 75 F. S

R 15 Control No cure in 7 days. 16 Benzothiazolyl disulfide Cure in 4 days. C- S-N 17 Z-mercaptobenzothiazole Cure in 4 days. 18 N-oxydiethylenebenzothiazole2- Cure in 1 day. R

sulfenamide. N 1% lliII-tgeohexylberigothiatzgle-asuienamidm gure 1in 1 gay. 2 iisopro y enzo iazo eure n4 ays.

sulienamld wherein R and R may be the same or different and when taken singly are selected from the group consist- In Examples 21-25, 100 parts by weight of LP-32 ing of alkyl, branched alkyl, and cycloalkyl groups were mixed with 30 parts by weight of calcium carbonate, and taken collectively with. the nitrogen atom to 9 which they are attached form an azaox-ahydrocarbon group.

2. A curable composition according to claim 1 Wherein the benzothiazole-2-sulfenamide is selected from the group consisting of: N-oxydiethylenebenzothiazole-Z-sulfenamide, N-cyclohexylbenzothiazole-2-sulfenamide, N,N- diisopropylbenzothiazole-2-sulfenamide, and N,N-diethylbenzothiazole-Z-sulfenamide.

3. A curable composition as in claim 1 in which at least one of said liquid polymers is a polysulfide polymercaptan polymer.

4. A curable composition as in claim 3 in which at least one of said oxidizing agents is zinc peroxide.

5. A curable composition as in claim 4 in which at least one of said co-curing agents is N-oxydiethylenebenzothiazole-Z-sulfenamide.

6. A curable composition as in claim 4 in which at least one of said co-curing agents is N-cyclohexylbenzothiazole- 2-sulfenamide.

7. A curable composition as in claim 1 in which at least one of said inorganic oxides is calcium peroxide.

8. A curable composition as in claim 7 in which at least one of said co-curing agents is N-cyclohexylbenzothiazole-Z-sulfenamide.

9. A curable composition as in claim 1 in which at least one of said inorganic oxides is manganese dioxide.

10. A curable composition as in claim 9 in which at least one of said co-curing agents is selected from N- oxydiethylenebenzothiazole 2-sulfenamide and N-cyclohexylbenzothiazole-2-sulfenamide.

11. A curable composition as in claim 1 is which at least one of said inorganic oxides is tellurium dioxide.

12. A curable composition as in claim 11 in which at least one of said co-curing agents is N-oxydiethylenebenzothiazole-2-sulfenamide.

13. A curable composition as in claim 1 in which at least one of said inorganic oxides is potassium iodate.

14. A curable'composition as in claim 13 in which at least one of said co-curing agents is N-oxydiethylenebenzothiazole-Z-sulfenamide.

References Cited UNITED STATES PATENTS OTHER REFERENCES Gaylord: Polyethers, Part III, Polyalkylene Sulfides and other Polythioethers, 1962, pp. 126-132.

Fettes et al.: Industrial and Engineering Chemistry, Mechanism of Vulcanization of Polysulfide Rubbers, vol. 46, No. 7, July 1954, p. 1539-1541.

DONALD E. CZAJA, Primary Examiner M. I. MARQUIS, Assistant Examiner US. 01. X.R. 

